CN113122087A - Water-based graphene oxide composite anticorrosive paint and preparation method thereof - Google Patents
Water-based graphene oxide composite anticorrosive paint and preparation method thereof Download PDFInfo
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- CN113122087A CN113122087A CN201911403666.0A CN201911403666A CN113122087A CN 113122087 A CN113122087 A CN 113122087A CN 201911403666 A CN201911403666 A CN 201911403666A CN 113122087 A CN113122087 A CN 113122087A
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- Prior art keywords
- graphene oxide
- water
- paint
- based composite
- composite anticorrosive
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- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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- C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
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- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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- Paints Or Removers (AREA)
Abstract
The invention provides a water-based composite anticorrosive paint film, namely a coating film, wherein graphene oxide sheets are uniformly and orderly arranged in a paint film structure to form a graphene oxide layer; the graphene oxide layer is in the paint film structure; the thickness direction of the graphene oxide layer is the same as or similar to the thickness direction of the paint film structure. In the film formed by the water-based composite anticorrosive paint, the graphene oxide can be uniformly and orderly distributed and is in parallel-like staggered distribution to form a labyrinth network interwoven by graphene oxide sheet layers, and the graphene oxide sheet layers are uniformly distributed in the whole paint film, so that the salt spray resistance of the paint is improved, and the paint has good anticorrosive performance, and the graphene oxide is low in consumption and good in anticorrosive performance. The graphene oxide anticorrosive paint provided by the invention is a single-component water-based paint, has extremely low VOC, is environment-friendly, is simple and convenient to operate, is convenient to construct, does not increase the improvement cost, and is easy to popularize and apply in a large scale.
Description
Technical Field
The invention belongs to the technical field of anticorrosive coatings, and relates to a water-based composite anticorrosive coating paint film, a water-based composite anticorrosive coating and a preparation method thereof, in particular to a water-based composite anticorrosive coating paint film, a water-based graphene oxide composite anticorrosive coating and a preparation method thereof.
Background
Graphene (Graphene), a new material with a single-layer sheet structure composed of carbon atoms, is a two-dimensional crystal composed of carbon atoms and having only one layer of atomic thickness, is the lightest and thinnest material and the toughest material currently entering the application field, and has an electron mobility of 2 × 10 at room temperature5cm2·V-1·s-11/300 is the speed of light, and the theoretical specific surface area can reach 2630m2 g-1The light absorption of the whole wave band is only 2.3 percent, and the heat conductivity is as high as 5000 W.m-1·K-1The Young modulus exceeds 1100GPa, the tensile strength exceeds 130GPa, the toughness is very good, when external mechanical force is applied, carbon atoms can adapt to external force through bending deformation without rearranging the carbon atoms, so that the stability of the structure is kept, the breaking strength of the composite material is 200 times higher than that of steel, the composite material has good elasticity, and the stretching amplitude can reach 20% of the size of the composite material; in addition, graphene is almost completely transparent, absorbs only 2.3% of light, and is very dense and impenetrable by even the smallest gas atoms (helium atoms). These characteristics make it very suitable for various disciplines and fields, and it is due to the excellent physicochemical properties of graphene, which is widely used in energy storage materials, environmental engineering, sensitive sensing, and is called "black gold" or "king of new materials", and has potential to be used in energy storage materials, environmental engineering, and sensitive sensingThe carbon material has wide application prospect, becomes a focus of attention and a research hotspot all over the world at present, is industrialized from the research stage about derivatives such as graphene and the like, causes wide participation of various industries, is a carbon material with very wide application potential, and particularly has huge application prospect in a plurality of emerging industries such as novel reaction separation, new materials, energy conservation and environmental protection.
With the new 'environmental protection law' coming off the counter, the collection of consumption tax and pollution discharge tax, and the importance of consumers on environmental protection, the environmental protection type water-based composite anticorrosive paint has come into great development opportunity. The water-based composite anticorrosive paint refers to a paint using water as a solvent or as a dispersion medium, and can be divided into two categories: natural water composite anticorrosive paint of natural substance or mineral matter (such as potassium silicate) and petrochemical water composite anticorrosive paint of synthetic resin (such as acrylic resin). Most of the commonly used and studied water-based composite anticorrosive coatings are synthetic resin-based ones.
In recent years, coating products containing graphene-based materials have been reported, but in practical applications, the graphene-based materials have many problems and restriction factors, such as easy agglomeration of the graphene-based materials. Because the graphene materials and the derivatives thereof have larger specific surface areas and stronger Van der Waals acting forces exist among each other, the agglomeration and winding phenomena are obvious, so that the graphene materials cannot be stably dispersed, and the graphene materials and the derivatives thereof are easy to agglomerate together again after dispersion and are difficult to open. And the graphene oxide needs to be modified, so that the preparation process is complex.
Therefore, how to find a more suitable way to apply the graphene materials to the field of the water-based composite anticorrosive paint better not only can solve the agglomeration defect of graphene itself, but also can better improve the performance of the paint becomes a problem to be solved urgently by a plurality of application manufacturers and a front-line research and development staff.
Disclosure of Invention
In the aqueous composite anticorrosive coating provided by the invention, graphene oxide can be uniformly and orderly distributed to form a labyrinth network with the distribution of graphene oxide sheets, so that the physical barrier and the establishment of a conductive network of the graphene oxide sheets are realized, the agglomeration of the graphene oxide is solved, and the performance of the aqueous composite anticorrosive coating is better improved.
The invention provides a water-based composite anticorrosive paint film, wherein graphene oxide sheets are uniformly and orderly arranged in the paint film structure to form a graphene oxide layer;
the graphene oxide layer is in the paint film structure;
the thickness direction of the graphene oxide layer is the same as or similar to the thickness direction of the paint film structure.
Preferably, viewed from the section of the paint film structure, along the thickness direction of the graphene oxide layer, adjacent or similar graphene oxide sheets in the graphene oxide layer are distributed in a staggered manner;
viewed from the section of the paint film structure, a graphene oxide layer with a labyrinth effect is formed between the graphene oxide sheets along the thickness direction of the graphene oxide layer;
the thickness directions are close, namely, the included angle between the thickness direction of the graphene oxide layer and the thickness direction of the paint film structure is less than or equal to 60 degrees;
the thickness of the graphene oxide sheet is 0.7-2 nm;
the number of graphene oxide sheets is 1-5;
the thickness of the paint film is 50-100 mu m.
The invention provides a water-based composite anticorrosive paint which comprises the following components in percentage by mass:
preferably, the auxiliary agent comprises one or more of a dispersing agent, a wetting agent, a defoaming agent, a neutralizing agent, a film forming auxiliary agent, an anti-flash rust auxiliary agent and a rheological auxiliary agent;
the addition amount of the dispersing agent is 1-5 parts by weight;
the addition amount of the wetting agent is 0.05-0.3 part by weight;
the addition amount of the defoaming agent is 0.1-0.5 part by weight;
the addition amount of the neutralizing agent is 0.3-0.6 part by weight;
the addition amount of the film-forming assistant is 3-8 parts by weight;
the flash rust resisting additive is added in an amount of 0.5-2 parts by weight;
the addition amount of the rheological additive is 0.5-2 parts by weight;
the mass content of the graphene oxide in the water-based composite anticorrosive paint is 0.1-3%;
the dispersant comprises one or more of KALD-104, KOOLY 756, KOOLY7166, Silok7195W and OROTAN 731A;
the wetting agent comprises one or more of TEGO Twin4100, CA-81, KSPW-101 and KSPW-132;
the antifoaming agent comprises one or more of TEGO 902w, TEGO 1488, KXDF-204, BYK-024, and KOOLY 3150;
the neutralizing agent AMP-95 and/or ammonia water;
the film forming auxiliary agent comprises one or more of DPM, DPnB and texnol;
the flash rust resisting auxiliary agent comprises one or more of initiator R-760F, Hostacor AC 18, Raybo 60, Lubrizol 2120 and SHYT 5179;
the rheological additive comprises one or more of RM-8W, RM-2020, RM-12W and KTGF-132;
the pigment and filler comprises one or more of zinc powder, iron oxide red, coarse whiting powder, titanium dioxide, antirust pigment, talcum powder, barite powder and mica powder.
Preferably, the graphene oxide allyl acid emulsion comprises graphene oxide, an acrylic polymerization monomer and a crosslinking monomer;
in a paint film of the water-based composite anticorrosive paint, the graphene oxide is embedded in a polymer formed by crosslinking the acrylic polymerization monomer and the crosslinking monomer;
the crosslinking monomer comprises an amide group-containing crosslinking monomer;
the graphite oxide allyl acid emulsion comprises the following components in percentage by mass:
preferably, the acrylic polymeric monomer comprises one or more of acrylic acid, methacrylic acid, acrylate ester and methacrylate ester;
the crosslinking monomer comprises one or more of acrylamide, N-methylolacrylamide and N, N-diacetone acrylamide;
the protective glue comprises one or more of polyvinyl alcohol, styrene-maleic anhydride copolymer, acrylate copolymer and acrylic acid-styrene copolymer;
the initiator comprises one or more of inorganic peroxide initiator, organic peroxide initiator, azo initiator and redox initiator;
the emulsifier comprises a reactive emulsifier and an anionic emulsifier.
Preferably, the acrylic polymeric monomer comprises one or more of acrylic acid, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, isooctyl methacrylate, and isobornyl methacrylate;
the initiator comprises one or more of potassium persulfate, ammonium persulfate, benzoyl peroxide, tert-butyl hydroperoxide and azobisisobutyronitrile;
the anionic emulsifier comprises one or more of carboxylate, sulfonate and sulfate;
the reactive emulsifier comprises one or more of acrylamide isopropyl sodium sulfonate, sulfate containing vinyl alcohol ether, sodium succinate containing vinyl alcohol ether sulfonic group and sodium hydroxy alkyl sulfonate containing vinyl ether;
the content of the graphene oxide in the aqueous graphene oxide dispersion liquid is 1-5%.
The invention provides a preparation method of a water-based composite anticorrosive paint, which comprises the following steps:
A) mixing a part of auxiliary agent and water, then adding pigment and filler, mixing again, and then grinding to obtain slurry;
B) and continuously mixing the slurry obtained in the step, the oxidized graphite allyl acrylic acid emulsion, the other part of the auxiliary agent and water to obtain the water-based composite anticorrosive paint.
Preferably, the part of the auxiliary agent comprises one or more of a dispersing agent, a wetting agent, a defoaming agent, a film forming auxiliary agent and a neutralizing agent;
the other part of the auxiliary agent comprises an anti-flash rust auxiliary agent and/or a rheological auxiliary agent;
the mixing comprises stirring and mixing at a low speed;
the mixing time is 5-15 minutes;
the mixing speed is 500-800 r/min;
the remixing comprises high-speed stirring and mixing;
the remixing time is 10-15 minutes;
the rotation speed of the remixing is 800-1200 r/min.
Preferably, the grinding time is 10-15 minutes;
the rotation speed of the grinding is 600-900 r/min;
the particle size after grinding is less than or equal to 30 mu m;
the continuous mixing comprises low-speed stirring and mixing;
the time for continuing mixing is 10-25 minutes;
the rotating speed of the continuous mixing is 600-800 r/min;
the viscosity of the water-based composite anticorrosive paint is 80-105 ku.
The invention provides a water-based composite anticorrosive paint film, namely a coating film, wherein graphene oxide sheets are uniformly and orderly arranged in a paint film structure to form a graphene oxide layer; the graphene oxide layer is in the paint film structure; the thickness direction of the graphene oxide layer is the same as or similar to the thickness direction of the paint film structure. Compared with the prior art, the invention aims at the problems of obvious agglomeration and winding phenomena, unstable dispersion, uneven distribution, complex modification process and the like in the existing graphene oxide modified water-based composite anticorrosive coating.
The invention particularly introduces the oxidized graphite allyl acid emulsion, and combines the auxiliary agent, the pigment and the filler with specific content and components. The film formed by the water-based composite anticorrosive paint has a special structure, graphene oxide can be uniformly and orderly distributed and is in parallel-like staggered distribution to form a labyrinth network interwoven by graphene oxide lamella, and the graphene oxide lamella is embedded in a polymer formed by crosslinking an acrylic polymerization monomer and a crosslinking monomer, so that the graphene oxide lamella can be uniformly distributed in the whole paint film, and the problem of agglomeration of the graphene oxide is solved; and the addition of the special crosslinking monomers improves the corrosion resistance and the conductivity of the emulsion, and the special crosslinking monomers and the emulsion complement each other, thereby laying a solid foundation for better improving the performance of the water-based composite anticorrosive paint.
According to the graphene oxide anticorrosive coating with the acrylic emulsion as the matrix, the graphene oxide and the special crosslinking monomer containing the amide group are introduced, the addition of the special crosslinking monomers improves the corrosion resistance and the conductivity of the coating, simultaneously, the amide group and the carboxyl group contained in the acrylic polymerization monomer are easy to crosslink after the amino group is lost after drying, and the crosslinked emulsion has good film forming property, high transparency, firm adhesion and good water resistance, compared with the common acrylic anticorrosive coating, the salt spray resistance of the coating is improved, the coating has good anticorrosive property, the graphene oxide consumption is small (0.1-3%), and the anticorrosive property is good. The graphene oxide anticorrosive paint provided by the invention is a single-component water-based paint, has extremely low VOC, is environment-friendly, simple and convenient to operate, is convenient to construct, is consistent with the traditional synthetic method, is simple and convenient to operate and easy to control, is stable in a graphene oxide acrylic acid emulsion product, does not increase the later improvement cost, and is easy to popularize and apply in a large scale.
Experimental results show that the graphene oxide anticorrosive paint provided by the invention has excellent water resistance which can reach 650-800 h and excellent salt spray resistance which can reach 450-500 h, and the acrylic resin anticorrosive paint without the graphene oxide is only 100h in water resistance and is only 48h in salt spray resistance. The invention can obviously improve the water resistance and salt spray resistance of the coating and embody good corrosion resistance.
Drawings
FIG. 1 is an SEM scanning electron microscope image of a paint film section of a water-based composite anticorrosive paint prepared in example 4 of the invention;
FIG. 2 is a scanning electron microscope image of a paint film section of the waterborne composite anticorrosive paint prepared in example 4 of the present invention;
FIG. 3 is an SEM scanning electron microscope image of a paint film section of the water-based composite anticorrosive paint prepared in example 5 of the invention;
FIG. 4 is an SEM scanning electron microscope image of a paint film section of the water-based composite anticorrosive paint prepared in example 6 of the invention.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
All of the starting materials of the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.
All the raw materials of the present invention are not particularly limited in their purity, and the present invention preferably employs the purity of conventional materials used in the field of analytical purification or aqueous acrylic resin coating.
The invention provides a water-based composite anticorrosive paint film, wherein graphene oxide sheets are uniformly and orderly arranged in the paint film structure to form a graphene oxide layer;
the graphene oxide layer is in the paint film structure;
the thickness direction of the graphene oxide layer is the same as or similar to the thickness direction of the paint film structure.
The definition of the paint film is not particularly limited by the present invention, and the paint film produced by the anticorrosive paint known to those skilled in the art can be selected and adjusted by those skilled in the art according to the actual application situation, the product requirement and the quality requirement, and the paint film produced by the water-based composite anticorrosive paint of the present invention is a coating produced by the water-based composite anticorrosive paint, and more preferably a coating obtained after the water-based composite anticorrosive paint is painted.
In the invention, in the paint film structure, graphene oxide sheets are flatly, uniformly and orderly arranged in the paint film structure to form a graphene oxide layer. The thickness of the graphene oxide layer is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to actual application conditions, product requirements and quality requirements. In the invention, the graphene oxide layers are uniformly distributed in the paint film from the upper surface of the paint film to the lower surface of the paint film, namely the thickness of the graphene oxide layers is the same as or similar to that of the paint film.
In the present invention. The thickness direction of the graphene oxide layer is the same as or similar to the thickness direction of the paint film structure, and more preferably the thickness direction of the graphene oxide layer is the same as the thickness direction of the paint film structure. In the plane of the paint film, the plane close to the substrate is the lower surface, and the plane far away from the substrate is the upper surface, i.e. the plane of the graphene oxide layer is basically the same as the plane of the paint film. In the present invention, the effect can also be achieved when the thickness direction of the graphene oxide layer is close to the thickness direction of the paint film structure, and to ensure the technical effect, the close specific preference is that an included angle between the thickness direction of the graphene oxide layer and the thickness direction of the paint film structure is less than or equal to 60 °, more preferably less than or equal to 50 °, more preferably less than or equal to 40 °, more preferably less than or equal to 30 °, more preferably less than or equal to 20 °, and more preferably less than or equal to 10 °.
The definition of the graphene oxide layer is not particularly limited in the present invention, and may be a graphene oxide layer known to those skilled in the art, and those skilled in the art can understand based on the basic general knowledge that, in the present invention, the graphene oxide layer is not a layer containing only graphene oxide, but is a graphene oxide layer obtained by uniformly distributing graphene oxide, and the whole paint film is a water-based acrylic resin, so that the graphene oxide layer is a mixed layer composed of graphene oxide and an acrylic resin material, or a mixed layer composed of graphene oxide, an acrylic resin and other materials. The graphene oxide layer contains graphene oxide sheets, and the microscopic two-dimensional lamellar structure of the graphene oxide sheets is combined with the graphene oxide layer formed macroscopically, so that the physical barrier and static conductive capability is favorably formed, and the corrosion resistance and the conductivity of the coating are improved.
The graphene oxide in the invention is preferably embedded in a polymer formed by crosslinking an acrylic polymerization monomer and a crosslinking monomer, and can also be regarded as graphene oxide sheets adsorbed in an acrylic resin matrix, so that the re-agglomeration of the graphene is avoided to a certain extent, the full utilization of the self performance of the graphene oxide is facilitated, and the comprehensive performance, the corrosion resistance, the static electricity conducting capacity and the like of the coating are enhanced.
In order to enable the graphene oxide sheets to have a physical shielding effect and also have better anti-corrosion and electrostatic conduction performances, viewed from the section of a paint film structure, adjacent or similar graphene oxide sheets in the graphene layer are distributed in a staggered mode along the thickness direction of the graphene layer, the staggered distribution of similar parallel types and the staggered distribution of cross type can be included, more preferably, the staggered distribution of similar parallel types and the staggered distribution of a small amount of cross type are mainly selected, and therefore the labyrinth effect is better realized. The definition of the section of the paint film structure is not particularly limited by the present invention, and the positional relationship of the section of the conventional coating, which is well known to those skilled in the art, can be selected and adjusted by those skilled in the art according to the actual application, product requirements and quality requirements, and those skilled in the art can understand that the section of the coating, that is, the section or the fracture surface in the thickness direction of the coating, is generated after the aqueous floor paint is sprayed on the substrate. Furthermore, in the paint film of the invention, when viewed from the section (section) of the paint film structure, along the thickness direction of the graphene layer (or paint film), graphene oxide layers with a labyrinth effect are formed between the graphene oxide sheets, that is, the graphene oxide layers are distributed in a staggered manner, mainly in a parallel-like staggered manner, and a small part of the graphene oxide layers are crossed to form a labyrinth-like graphene oxide layer. Moreover, the graphene oxide sheets are distributed in an orderly and staggered manner, and contact exists among partial graphene oxide sheets, so that a conductive net and a physical barrier layer are formed.
In the invention, in order to ensure the comprehensive performance of the aqueous composite anticorrosive coating and improve the anticorrosive performance of the aqueous composite anticorrosive coating, the graphene oxide preferably comprises one or more of a single-layer graphene oxide material, a few-layer graphene oxide material and a multi-layer graphene oxide material, and more preferably comprises the single-layer graphene oxide and/or the few-layer graphene oxide material. Specifically, the number of sheets of the graphene oxide-based material is preferably 1 to 5, may be 2 to 4, or 1 to 3, and more specifically, the ratio of the graphene oxide having 5 or less sheets is preferably 80% or more, more preferably 85% or more, and more preferably 90% or more. The thickness of the graphene oxide sheet layer is preferably 0.7-2 nm, more preferably 1.0-1.8 nm, and more preferably 1.2-1.5 nm. The sheet diameter of the graphene oxide sheet layer is preferably 7-20 μm, more preferably 10-18 μm, and more preferably 12-15 μm. The specific surface area of the graphene oxide is preferably 400-600 m2(ii)/g, more preferably 420 to 580m2(iv)/g, more preferably 450 to 550m2/g。
The thickness of the paint film is not particularly limited in principle, and can be selected and adjusted by technicians in the field according to actual application conditions, composite conditions and product performance, in order to ensure the comprehensive performance of the water-based composite anticorrosive paint and improve the anticorrosive performance of the water-based composite anticorrosive paint, the thickness of the paint film is preferably 50-100 micrometers, more preferably 60-90 micrometers and more preferably 70-80 micrometers under the condition of ensuring the requirements of the water-based composite anticorrosive paint due to the matching of the graphene oxide and various additives.
The invention provides a water-based composite anticorrosive paint which comprises the following components in percentage by mass:
the selection and composition of the structure in the water-based composite anticorrosive paint and the corresponding optimization principle can be corresponding to the selection and composition of the raw materials in the paint film of the water-based composite anticorrosive paint and the corresponding optimization principle, and are not described in detail herein.
In the water-based composite anticorrosive paint, the addition amount of water is 5-15 parts by weight, preferably 6-14 parts by weight, more preferably 7-13 parts by weight, more preferably 8-12 parts by weight, and more preferably 9-11 parts by weight. In the water-based composite anticorrosive coating, the addition amount of the graphene oxide acrylic acid emulsion is 45-80 parts by weight, preferably 50-75 parts by weight, more preferably 55-70 parts by weight, and more preferably 60-65 parts by weight. In the water-based composite anticorrosive coating, the addition amount of the pigment and filler is 30-60 parts by weight, preferably 35-55 parts by weight, and more preferably 40-50 parts by weight. In the water-based composite anticorrosive paint, the addition amount of the auxiliary agent is 5.5-18 parts by weight, preferably 8-15 parts by weight, and more preferably 10-13 parts by weight.
The specific selection of the assistant is not particularly limited in principle, and a person skilled in the art can select and adjust the assistant according to actual production conditions, product requirements and quality requirements.
The addition amount and specific selection of the dispersing agent are not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to actual application conditions, product requirements and quality requirements, in order to enable graphene oxide to be distributed uniformly and in a staggered manner better, ensure that a graphene oxide acrylic acid emulsion in the water-based composite anticorrosive coating is fully crosslinked, facilitate film formation and further improve the comprehensive performance and the anticorrosive performance of the water-based composite anticorrosive coating, the addition amount of the dispersing agent is preferably 1-5 parts by weight, more preferably 1.5-4.5 parts by weight, more preferably 2-4 parts by weight, and more preferably 2.5-3.5 parts by weight. The dispersant preferably comprises one or more of KALD-104, KOOLY 756, KOOLY7166, Silok7195W and OROTAN 731A, more preferably KALD-104, KOOLY 756, KOOLY7166, Silok7195W or OROTAN 731A.
The addition amount and specific selection of the wetting agent are not particularly limited in principle, and a person skilled in the art can select and adjust the wetting agent according to actual application conditions, product requirements and quality requirements, in order to enable graphene oxide to be distributed uniformly and in a staggered mode better, ensure that graphene oxide acrylic acid emulsion in the water-based composite anticorrosive paint is fully crosslinked, facilitate film formation and further improve comprehensive performance and anticorrosive performance of the water-based composite anticorrosive paint, the addition amount of the wetting agent is preferably 0.05-0.3 part by weight, more preferably 0.1-0.25 part by weight, and more preferably 0.15-0.2 part by weight. The wetting agent preferably comprises one or more of TEGO Twen 4100, CA-81, KSPW-101 and KSPW-132, more preferably TEGO Twen 4100, CA-81, KSPW-101 or KSPW-132.
The addition amount and specific selection of the defoaming agent are not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to actual application conditions, product requirements and quality requirements, in order to enable graphene oxide to be distributed uniformly and in a staggered manner better, ensure that the graphene oxide acrylic acid emulsion in the water-based composite anticorrosive paint is fully crosslinked, facilitate film formation and further improve the comprehensive performance and the anticorrosive performance of the water-based composite anticorrosive paint, the addition amount of the defoaming agent is preferably 0.1-5 parts by weight, more preferably 0.6-4.5 parts by weight, more preferably 1.1-4 parts by weight, more preferably 1.6-3.5 parts by weight, and more preferably 2.1-3 parts by weight. The defoamer preferably comprises one or more of TEGO 902w, TEGO 1488, KXDF-204, BYK-024, and KOOLY3150, more preferably TEGO 902w, TEGO 1488, KXDF-204, BYK-024, or KOOLY 3150.
The addition amount and specific selection of the neutralizer are not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to actual application conditions, product requirements and quality requirements, in order to enable graphene oxide to be distributed uniformly and in a staggered mode better, ensure that the graphene oxide acrylic acid emulsion in the water-based composite anticorrosive paint is fully crosslinked, facilitate film formation and further improve the comprehensive performance and the anticorrosive performance of the water-based composite anticorrosive paint, the addition amount of the neutralizer is preferably 0.3-0.6 part by weight, more preferably 0.35-0.55 part by weight, and more preferably 0.4-0.5 part by weight. The neutralizing agent preferably comprises AMP-95 and/or aqueous ammonia, more preferably AMP-95 or aqueous ammonia.
The addition amount and specific selection of the film-forming assistant are not particularly limited in principle, and a person skilled in the art can select and adjust the film-forming assistant according to actual application conditions, product requirements and quality requirements, in order to enable graphene oxide to be distributed uniformly and in a staggered mode better, ensure that graphene oxide acrylic acid emulsion in the water-based composite anticorrosive paint is fully crosslinked, facilitate film formation, and further improve comprehensive performance and anticorrosive performance of the water-based composite anticorrosive paint, the addition amount of the film-forming assistant is preferably 3-8 parts by weight, more preferably 4-7 parts by weight, and more preferably 5-6 parts by weight. The coalescent preferably comprises one or more of DPM, DPnB and texnol, more preferably DPM, DPnB or texnol.
The addition amount and specific selection of the flash rust resisting auxiliary agent are not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to actual application conditions, product requirements and quality requirements, in order to enable graphene oxide to be distributed uniformly and in a staggered mode better, ensure that a graphene oxide acrylic acid emulsion in the water-based composite anticorrosive paint is fully crosslinked, facilitate film formation and further improve comprehensive performance and anticorrosive performance of the water-based composite anticorrosive paint, the addition amount of the flash rust resisting auxiliary agent is preferably 0.5-2 parts by weight, more preferably 0.7-1.8 parts by weight, more preferably 0.9-1.6 parts by weight, and more preferably 1.1-1.4 parts by weight. The flash rust resisting auxiliary agent preferably comprises one or more of initiator R-760F, Hostacor AC 18, Raybo 60, Lubrizol 2120 and SHYT5179, more preferably initiator R-760F, Hostacor AC 18, Raybo 60, Lubrizol 2120 or SHYT 5179.
The addition amount and specific selection of the rheological additive are not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to actual application conditions, product requirements and quality requirements, in order to enable graphene oxide to be distributed uniformly and in a staggered manner better, ensure that a graphene oxide acrylic acid emulsion in the water-based composite anticorrosive paint is fully crosslinked, facilitate film formation and further improve the comprehensive performance and the anticorrosive performance of the water-based composite anticorrosive paint, the addition amount of the rheological additive is preferably 0.5-2 parts by weight, more preferably 0.7-1.8 parts by weight, more preferably 0.9-1.6 parts by weight, and more preferably 1.1-1.4 parts by weight. The rheological aid preferably comprises one or more of RM-8W, RM-2020, RM-12W and KTGF-132, more preferably RM-8W, RM-2020, RM-12W or KTGF-132.
The pigment and filler is preferably selected from one or more of zinc powder, iron oxide red, triple superphosphate powder, titanium dioxide powder, antirust pigment, talcum powder, barite powder and mica powder, and more preferably selected from zinc powder, iron oxide red, triple superphosphate powder, titanium dioxide powder, antirust pigment, talcum powder, barite powder or mica powder.
The source of the graphene oxide acrylic emulsion film is not particularly limited in principle, and a person skilled in the art can select and adjust the film according to the actual application condition, the product requirement and the quality requirement. In the paint film of the water-based composite anticorrosive paint, the graphene oxide is preferably embedded in a polymer formed by crosslinking the acrylic polymer monomer and the crosslinking monomer.
More specifically, the graphite oxide allyl acid emulsion of the present invention comprises, by mass fraction:
the selection of the crosslinking monomer is not particularly limited in principle, and a person skilled in the art can select and adjust the crosslinking monomer according to the actual application situation, the product requirements and the quality requirements.
The special combination structure of the graphene oxide/allyl acid emulsion enables graphene oxide to be uniformly distributed, reduces agglomeration, can achieve a better conductive effect due to a three-dimensional network in staggered distribution, and further improves the corrosion resistance and conductivity of the emulsion by combining with the addition of a special crosslinking monomer, thereby improving the performance of the water-based composite anticorrosive coating.
In the graphene oxide allyl acid emulsion, the addition amount of the styrene is 0-20 parts by weight, preferably 2-18 parts by weight, more preferably 5-15 parts by weight, and more preferably 8-12 parts by weight.
In the graphene oxide allyl acid emulsion, the addition amount of the crosslinking monomer is 0.1-5 parts by weight, preferably 0.5-4.5 parts by weight, more preferably 1-4 parts by weight, more preferably 1.5-3.5 parts by weight, and more preferably 2-3 parts by weight. The specific selection of the crosslinking monomer is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to the actual application situation, the product requirements and the quality requirements.
In the graphene oxide acrylic acid emulsion, the addition amount of the acrylic acid polymerization monomer is 10-40 parts by weight, preferably 12-38 parts by weight, more preferably 15-35 parts by weight, more preferably 18-32 parts by weight, and more preferably 20-30 parts by weight. The concrete selection of the acrylic polymeric monomer is not particularly limited in principle, and can be selected and adjusted by those skilled in the art according to the actual application situation, the product requirements and the quality requirements, in order to enable the graphene oxide to be distributed uniformly and staggeredly better, ensure that the graphene oxide acrylic acid emulsion in the water-based composite anticorrosive coating is fully crosslinked, facilitate film formation and further improve the comprehensive performance and the anticorrosive performance of the water-based composite anticorrosive coating, the acrylic polymeric monomer preferably comprises one or more of acrylic acid, methacrylic acid, acrylic ester and methacrylic ester, more preferably comprises one or more of acrylic acid, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, isooctyl methacrylate and isobornyl methacrylate, and more preferably comprises acrylic acid, methacrylic acid, acrylic acid, Methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, isooctyl methacrylate or isobornyl methacrylate, more preferably one or more of methacrylic acid, butyl methacrylate, isooctyl methacrylate and methyl methacrylate.
In the graphene oxide allyl acid emulsion, the addition amount of the protective adhesive is 5-15 parts by weight, preferably 6-14 parts by weight, more preferably 7-13 parts by weight, more preferably 8-12 parts by weight, and more preferably 9-11 parts by weight. The invention has no special restriction on the specific selection of the protective adhesive in principle, and the technical personnel in the field can select and adjust the protective adhesive according to the actual application condition, the product requirement and the quality requirement, in order to ensure that the graphene oxide can be better and uniformly distributed in a staggered way, ensure that the graphene oxide acrylic acid emulsion in the water-based composite anticorrosive coating is fully crosslinked, be conductive to film formation, further improve the comprehensive performance and the anticorrosive performance of the water-based composite anticorrosive coating, the protective glue preferably comprises one or more of polyvinyl alcohol, styrene-maleic anhydride copolymer, acrylate copolymer and acrylic acid-styrene copolymer, more preferably polyvinyl alcohol, styrene-maleic anhydride copolymer, acrylate copolymer or acrylic acid-styrene copolymer, and more preferably acrylate copolymer or acrylic acid-styrene copolymer.
In the graphene oxide allyl acid emulsion, the addition amount of the initiator is 0.1-5 parts by weight, preferably 0.5-4.5 parts by weight, more preferably 1-4 parts by weight, more preferably 1.5-3.5 parts by weight, and more preferably 2-3 parts by weight. The specific selection of the initiator is not particularly limited in principle, and a person skilled in the art can select and adjust the initiator according to the actual application situation, the product requirements and the quality requirements. More specifically, the inorganic peroxide initiator preferably includes potassium persulfate and/or ammonium persulfate; the organic peroxide initiator preferably comprises benzoyl peroxide and/or tert-butyl hydroperoxide; the azo-based initiator preferably includes azobisisobutyronitrile. The initiator of the present invention preferably comprises one or more of potassium persulfate, ammonium persulfate, benzoyl peroxide, tert-butyl hydroperoxide and azobisisobutyronitrile, more preferably potassium persulfate, ammonium persulfate, benzoyl peroxide, tert-butyl hydroperoxide or azobisisobutyronitrile, and more preferably ammonium sulfate or potassium persulfate.
In the graphene oxide allyl acid emulsion, the addition amount of the emulsifier is 0.1-5 parts by weight, preferably 0.5-4.5 parts by weight, more preferably 1-4 parts by weight, more preferably 1.5-3.5 parts by weight, and more preferably 2-3 parts by weight. The invention has no particular limitation on the specific selection of the emulsifier in principle, and a person skilled in the art can select and adjust the emulsifier according to the actual application condition, the product requirement and the quality requirement.
More specifically, the anionic emulsifier preferably includes one or more of carboxylate, sulfonate and sulfate salt, more preferably carboxylate, sulfonate or sulfate salt, and more preferably sodium alkyl diphenyl oxide disulfonate, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate and alkylphenol polyoxyethylene ether sulfate. The reactive emulsifier preferably comprises one or more of acrylamide isopropyl sodium sulfonate, vinyl alcohol ether sulfate, vinyl alcohol ether sulfonic succinate sodium salt and vinyl ether hydroxyalkyl sodium sulfonate, more preferably acrylamide isopropyl sodium sulfonate, vinyl alcohol ether sulfate, vinyl alcohol ether sulfonic succinate sodium salt or vinyl ether hydroxyalkyl sodium sulfonate, and further specifically, the reactive emulsifier is preferably prepared by mutually matching alkylphenol polyoxyethylene ether sulfate and vinyl ether hydroxyalkyl sodium sulfonate, and the specific mass ratio can be 1: 1.
in the graphene oxide allyl acid emulsion, the addition amount of the aqueous graphene oxide dispersion liquid is 40-70 parts by weight, preferably 42-68 parts by weight, more preferably 45-65 parts by weight, more preferably 48-63 parts by weight, and more preferably 50-60 parts by weight. The invention has no particular limitation on the specific parameters of the aqueous graphene dispersion liquid in principle, and a person skilled in the art can select and adjust the parameters according to the actual application situation, the product requirements and the quality requirements, in order to ensure that the graphene oxide can be better and uniformly distributed in a staggered manner, ensure that the graphene oxide acrylic acid emulsion in the aqueous composite anticorrosive paint is fully crosslinked, facilitate film formation and further improve the comprehensive performance and the anticorrosive performance of the aqueous composite anticorrosive paint, the content of the graphene oxide in the aqueous graphene oxide dispersion liquid is preferably 0.1-5%, more preferably 0.5-4.5%, more preferably 1-4%, more preferably 1.5-3.5%, more preferably 2-3%.
The invention also provides a preparation method of the oxidized graphite allyl acid emulsion, which comprises the following steps:
1) premixing styrene, a crosslinking monomer and an acrylic acid polymerization monomer to obtain a mixture A;
heating the aqueous graphene dispersion liquid, adding a protective adhesive and an emulsifier, and mixing to obtain a mixture B;
2) and slowly adding the mixture A and the initiator obtained in the step into the mixture B, and reacting to obtain the graphite oxide allyl acid emulsion.
The selection and composition of the raw materials required in the preparation process and the corresponding preferred principle can correspond to the selection and composition of the raw materials corresponding to the graphite oxide allyl acrylate emulsion and the corresponding preferred principle, and are not described in detail herein.
Firstly, premixing styrene, a crosslinking monomer and an acrylic acid polymerization monomer to obtain a mixture A; and heating the aqueous graphene dispersion liquid, adding a protective adhesive and an emulsifier, and mixing to obtain a mixture B.
The temperature for raising the temperature is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to actual production conditions, product requirements and quality requirements, in order to enable graphene oxide to be distributed uniformly and in a staggered mode better, ensure that the graphene oxide acrylic acid emulsion in the water-based composite anticorrosive coating is fully crosslinked, facilitate film formation and further improve the comprehensive performance and the anticorrosive performance of the water-based composite anticorrosive coating, the temperature for raising the temperature is preferably 75-95 ℃, more preferably 78-92 ℃, and more preferably 80-90 ℃.
The mixing mode is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to actual production conditions, product requirements and quality requirements.
The specific mixing process is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to actual production conditions, product requirements and quality requirements, in order to ensure that graphene oxide can be well and uniformly distributed in a staggered manner, ensure that the graphene oxide acrylic acid emulsion in the water-based composite anticorrosive coating is fully crosslinked, facilitate film formation and further improve the comprehensive performance and the anticorrosive performance of the water-based composite anticorrosive coating, the specific mixing steps are preferably as follows:
and heating the aqueous graphene oxide dispersion liquid, adding a protective adhesive for first mixing, adding an emulsifier for second mixing, and obtaining a mixture B.
The first mixing mode is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to actual production conditions, product requirements and quality requirements, in order to enable graphene oxide to be distributed uniformly and staggeredly better, ensure that the graphene oxide acrylic acid emulsion in the water-based composite anticorrosive coating is fully crosslinked, facilitate film formation and further improve the comprehensive performance and anticorrosive performance of the water-based composite anticorrosive coating, the first mixing mode preferably comprises ultrasonic stirring, and more preferably comprises ultrasonic stirring until dissolution.
The second mixing mode is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to actual production conditions, product requirements and quality requirements, in order to enable graphene oxide to be distributed uniformly and staggeredly better, ensure that the graphene oxide acrylic acid emulsion in the water-based composite anticorrosive coating is fully crosslinked, facilitate film formation and further improve the comprehensive performance and anticorrosive performance of the water-based composite anticorrosive coating, the second mixing mode preferably comprises ultrasonic stirring, more preferably ultrasonic stirring until dissolution, and more preferably ultrasonic stirring until complete dissolution.
According to the invention, the mixture A and the initiator obtained in the step are slowly added into the mixture B for reaction to obtain the graphene oxide acrylic acid emulsion.
The specific mode and parameters of slow addition are not particularly limited in principle, and a person skilled in the art can select and adjust the mode according to actual production conditions, product requirements and quality requirements. Specifically, the dripping speed is preferably 10-150 g/min, more preferably 30-120 g/min, more preferably 50-100 g/min, and more preferably 70-90 g/min. The dripping time is preferably 2-2.5 h, more preferably 2.1-2.4 h, and more preferably 2.2-2.3 h.
The specific parameters of the reaction are not particularly limited in principle, and a person skilled in the art can select and adjust the reaction parameters according to actual production conditions, product requirements and quality requirements, in order to enable graphene oxide to be distributed uniformly and in a staggered manner better, ensure that the graphene oxide acrylic acid emulsion in the water-based composite anticorrosive coating is fully crosslinked, facilitate film formation, and further improve the comprehensive performance and the anticorrosive performance of the water-based composite anticorrosive coating, the reaction temperature is preferably 75-95 ℃, more preferably 78-93 ℃, more preferably 80-90 ℃, and more preferably 82-88 ℃. The reaction time is preferably 2-10 h, more preferably 3-9 h, more preferably 4-8 h, and more preferably 5-7 h.
The method is a complete and refined production process, so that the graphene oxide can be well and uniformly distributed in a staggered manner, the full crosslinking of the graphene oxide acrylic acid emulsion in the water-based composite anticorrosive paint is ensured, the film forming is facilitated, the comprehensive performance and the anticorrosive performance of the water-based composite anticorrosive paint are further improved, and the method preferably further comprises a cooling step after the reaction.
The cooling step of the invention is preferably as follows:
and firstly cooling to the first temperature, removing residual monomers, and then continuously cooling to obtain the graphite oxide allyl acid emulsion. More preferably, the temperature is reduced to the first temperature, tert-butyl hydroperoxide is added to remove residual monomers, and then the temperature is reduced continuously to obtain the graphene oxide acrylic acid emulsion.
The specific parameters of the first temperature are not particularly limited in principle, and a person skilled in the art can select and adjust the parameters according to actual production conditions, product requirements and quality requirements, in order to enable graphene oxide to be distributed uniformly and in a staggered manner better, ensure that the graphene oxide acrylic acid emulsion in the water-based composite anticorrosive coating is fully crosslinked, facilitate film formation, and further improve the comprehensive performance and the anticorrosive performance of the water-based composite anticorrosive coating, the first temperature is preferably 55-65 ℃, more preferably 57-63 ℃, and more preferably 59-61 ℃.
In order to ensure that the graphene oxide can be well and uniformly distributed in a staggered manner, ensure that the graphene oxide acrylic acid emulsion in the water-based composite anticorrosive paint is fully crosslinked, facilitate film formation, further improve the comprehensive performance and the anticorrosive performance of the water-based composite anticorrosive paint, and complete and detailed preparation process, the preparation method can specifically comprise the following steps:
(1) uniformly mixing all the components in the first component to obtain a solution A;
(2) adding aqueous graphene dispersion liquid into a reaction container, heating to 75-95 ℃, adding protective glue, and ultrasonically stirring until the protective glue is dissolved;
(3) adding an emulsifier into the reaction container, and ultrasonically stirring until the emulsifier is completely dissolved;
(4) simultaneously dripping the solution A and the initiator into the reaction container, finishing the dripping at a constant speed within 2-2.5 h, and preserving the temperature for 30min after the dripping is finished;
(5) and (5) cooling and discharging.
In the step (5), preferably, the temperature is reduced to 70 ℃, tert-butyl hydroperoxide and the like are added to remove residual monomers, and then the temperature is reduced and the material is discharged.
The invention also provides a preparation method of the water-based composite anticorrosive paint, which comprises the following steps:
A) mixing a part of auxiliary agent and water, then adding pigment and filler, mixing again, and then grinding to obtain slurry;
B) and continuously mixing the slurry obtained in the step, the oxidized graphite allyl acrylic acid emulsion, the other part of the auxiliary agent and water to obtain the water-based composite anticorrosive paint.
The selection and composition of the raw materials in the preparation method, and the corresponding preferred principle, and the selection and composition of the raw materials corresponding to the aqueous composite anticorrosive paint, and the corresponding preferred principle can all be corresponded, and are not described in detail herein.
According to the invention, a part of auxiliary agent and water are mixed, then pigment and filler are added, and after mixing again, grinding is carried out to obtain the slurry.
The specific selection of the part of the auxiliary agents is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to actual production conditions, product requirements and quality requirements.
The specific mode and parameters of the mixing are not particularly limited in principle, and a person skilled in the art can select and adjust the mixing according to the actual production condition, the product requirement and the quality requirement. The mixing time is preferably 5 to 15 minutes, more preferably 7 to 13 minutes, and still more preferably 9 to 11 minutes. The mixing speed is preferably 500-800 r/min, more preferably 550-750 r/min, and more preferably 600-700 r/min.
The specific mode and parameters of the remixing are not particularly limited in principle, and a person skilled in the art can select and adjust the mode according to the actual production condition, the product requirement and the quality requirement. The remixing time is preferably 10 to 15 minutes, more preferably 11 to 14 minutes, and still more preferably 12 to 13 minutes. The rotation speed of the remixing is preferably 800-1200 r/min, more preferably 850-1150 r/min, more preferably 900-1100 r/min, and more preferably 950-1050 r/min.
The specific mode and parameters of the grinding are not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to actual production conditions, product requirements and quality requirements. The grinding time is preferably 10-15 minutes, more preferably 11-14 minutes, and more preferably 12-13 minutes. The rotation speed of the grinding is preferably 600 to 900r/min, more preferably 650 to 850r/min, and more preferably 700 to 800 r/min. The particle size of the ground raw material is less than or equal to 30 μm, more preferably less than or equal to 20 μm, more preferably less than or equal to 10 μm, and specifically may be 1-30 μm, or 3-20 μm, or 5-10 μm.
And finally, continuously mixing the slurry obtained in the step, the oxidized graphite allyl acid emulsion, the other part of the auxiliary agent and water to obtain the water-based composite anticorrosive paint.
The specific selection of the other part of the auxiliary agent is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to actual production conditions, product requirements and quality requirements.
The specific mode and parameters of the continuous mixing are not particularly limited in principle, and a person skilled in the art can select and adjust the continuous mixing mode and parameters according to actual production conditions, product requirements and quality requirements. The time for continuing the mixing is preferably 10 to 25 minutes, more preferably 12 to 23 minutes, and still more preferably 15 to 20 minutes. The rotation speed of the continuous mixing is preferably 600-800 r/min, more preferably 620-780 r/min, and more preferably 650-750 r/min.
The invention is a complete and refined integral process, so that graphene oxide can be well and uniformly distributed in a staggered manner, the graphene oxide acrylic acid emulsion in the water-based composite anticorrosive paint is fully crosslinked, the film forming is facilitated, the comprehensive performance and the anticorrosive performance of the water-based composite anticorrosive paint are further improved, and the viscosity of the water-based composite anticorrosive paint is preferably 80-105 ku, more preferably 85-100 ku, and more preferably 90-95 ku.
The invention is a complete and refined integral process, so that graphene oxide can be better and uniformly distributed in a staggered manner, the full crosslinking of the graphene oxide acrylic acid emulsion in the water-based composite anticorrosive paint is ensured, the film forming is facilitated, and the comprehensive performance and the anticorrosive performance of the water-based composite anticorrosive paint are further improved, and the preparation method of the water-based composite anticorrosive paint can specifically comprise the following steps:
step 1, adding a dispersing agent, a wetting agent, a defoaming agent, a film-forming assistant and a neutralizing agent into a water solvent, and stirring at a low speed respectively without splashing the materials;
slowly adding pigments and fillers, paying attention to avoid serious dust raising and powder accumulation, and washing the powder on the wall of the cylinder with a small amount of clear water; dispersing for 10-15 minutes at a high speed, then feeding the mixture into a sand mill, grinding the mixture to a fineness of less than 30um, feeding the mixture into a paint mixing kettle, cleaning a pull cylinder and the sand mill by using the residual deionized water, and feeding the cleaning solution into the paint mixing kettle after sand milling;
step 3, adding the graphene oxide and allyl acid composite emulsion into a paint mixing kettle, slowly adding the flash rust resisting auxiliary agent and the rheological auxiliary agent, stirring at a low speed for 5-15 minutes without splashing the materials, adding water to adjust to a proper viscosity, and continuously stirring at a low speed for 5-10 minutes until no obvious bubbles exist;
and 4, filtering and packaging to obtain the water-based composite anticorrosive paint.
The invention provides a water-based composite anticorrosive paint film, a water-based graphene oxide composite anticorrosive paint and a preparation method thereof. The invention introduces the oxidized graphite allyl acrylic acid emulsion, combines with the auxiliary agent, the pigment and the filler with specific content and components, and the like. The paint film formed by the water-based composite anticorrosive paint has a special structure, graphene oxide can be uniformly and orderly distributed and is in parallel-like staggered distribution to form a labyrinth network interwoven with graphene oxide lamella, and the graphene oxide lamella is embedded in a polymer formed by crosslinking an acrylic polymerization monomer and a crosslinking monomer, so that the graphene oxide lamella can be uniformly distributed in the whole film, and the problem of agglomeration of the graphene oxide is solved; and the addition of the special crosslinking monomers improves the corrosion resistance and the conductivity of the emulsion, and the special crosslinking monomers and the emulsion complement each other, thereby laying a solid foundation for better improving the performance of the water-based composite anticorrosive paint.
According to the graphene oxide anticorrosive coating with the acrylic emulsion as the matrix, the graphene oxide and the special crosslinking monomers containing amide groups are introduced, and the special crosslinking monomers are added and combined with the specific auxiliary agent, the pigment and the filler and the corresponding proportion, so that the labyrinth-type uniform distribution of graphene sheets in a paint film of the graphene oxide anticorrosive coating is further facilitated, and the corrosion resistance and the conductivity of the coating are improved; meanwhile, the amido and the carboxyl contained in the acrylic polymer monomer are easy to crosslink after being dried and losing the amido, and the crosslinked emulsion has good film forming property, high transparency, firm adhesion and good water resistance, compared with the common acrylic anticorrosive coating, the salt spray resistance of the coating is improved, the coating has good anticorrosive property, the graphene oxide consumption is less (0.1-3%), and the anticorrosive property is good.
The graphene oxide anticorrosive paint provided by the invention has the advantages that the physical barrier layer is formed between the metal matrix and the active medium, so that the diffusion and permeation are prevented, the thermal stability, the chemical stability and the tribological performance are good, and the mechanical performance and the anticorrosive performance are good. The preparation method is a single-component water-based paint, has extremely low VOC, is environment-friendly, is simple and convenient to operate, is convenient to construct, is consistent with the traditional synthetic method, is simple and convenient to operate and easy to control, is stable in the product of the oxidized graphite allyl acid emulsion, does not increase the later improvement cost, and is easy to popularize and apply in a large scale.
Experimental results show that the graphene oxide anticorrosive paint provided by the invention has excellent water resistance which can reach 650-800 h and excellent salt spray resistance which can reach 450-500 h, and the acrylic resin anticorrosive paint without the graphene oxide is only 120h in water resistance and is only 48h in salt spray resistance. The invention can obviously improve the water resistance and salt spray resistance of the coating and embody good corrosion resistance.
For further illustration of the present invention, the following examples are provided to describe a water-based composite anticorrosive paint film, a water-based composite anticorrosive paint and a preparation method thereof in detail, but it should be understood that the examples are carried out on the premise of the technical scheme of the present invention, and the detailed embodiments and specific operation procedures are given, only for further illustration of the features and advantages of the present invention, not for limitation of the claims of the present invention, and the protection scope of the present invention is not limited to the following examples.
Example 1
Referring to table 1, table 1 is a table of formulations of the graphene oxide acrylic acid emulsion prepared in examples 1 to 3 of the present invention.
TABLE 1
Referring to table 2, table 2 is a table of components of the graphene oxide acrylic emulsion prepared in examples 1 to 3 of the present invention.
TABLE 2
In examples 1 to 3, the emulsifier is used in a mass ratio of 1: 1 and sodium vinyl ether hydroxyl alkyl sulfonate.
The preparation method of the graphene oxide allyl acid emulsion provided in table 1 and table 2 comprises the following steps:
(1) uniformly mixing all the components in the first component to obtain a solution A;
(2) adding aqueous graphene oxide dispersion liquid into a reaction container, heating to 75-95 ℃, adding protective glue, and ultrasonically stirring until the protective glue is dissolved;
(3) adding an emulsifier into the reaction container, and ultrasonically stirring until the emulsifier is completely dissolved;
(4) simultaneously dripping the solution A and the initiator into the reaction container, finishing the dripping at a constant speed within 2-2.5 h, and preserving the temperature for 30min after the dripping is finished;
(5) and (5) cooling and discharging.
In the step (5), preferably, the temperature is reduced to 70 ℃, tert-butyl hydroperoxide and the like are added to remove residual monomers, and then the temperature is reduced and the material is discharged.
Example 2
The preparation method of the graphene oxide allyl acid emulsion provided in table 1 comprises the following steps:
(1) uniformly mixing all the components in the first component to obtain a solution A;
(2) adding aqueous graphene oxide dispersion liquid into a reaction container, heating to 75-95 ℃, adding protective glue, and ultrasonically stirring until the protective glue is dissolved;
(3) adding an emulsifier into the reaction container, and ultrasonically stirring until the emulsifier is completely dissolved;
(4) simultaneously dripping the solution A and the initiator into the reaction container, finishing the dripping at a constant speed within 2-2.5 h, and preserving the temperature for 30min after the dripping is finished;
(5) and (5) cooling and discharging.
In the step (5), preferably, the temperature is reduced to 70 ℃, tert-butyl hydroperoxide and the like are added to remove residual monomers, and then the temperature is reduced and the material is discharged.
Example 3
The preparation method of the graphene oxide allyl acid emulsion provided in table 1 comprises the following steps:
(1) uniformly mixing all the components in the first component to obtain a solution A;
(2) adding aqueous graphene oxide dispersion liquid into a reaction container, heating to 75-95 ℃, adding protective glue, and ultrasonically stirring until the protective glue is dissolved;
(3) adding an emulsifier into the reaction container, and ultrasonically stirring until the emulsifier is completely dissolved;
(4) simultaneously dripping the solution A and the initiator into the reaction container, finishing the dripping at a constant speed within 2-2.5 h, and preserving the temperature for 30min after the dripping is finished;
(5) and (5) cooling and discharging.
In the step (5), preferably, the temperature is reduced to 70 ℃, tert-butyl hydroperoxide and the like are added to remove residual monomers, and then the temperature is reduced and the material is discharged.
Example 4
The graphite oxide allyl acid emulsion prepared in example 1 of the present invention was used.
Step 1, adding 2.4 parts of dispersing agent, 0.14 part of wetting agent, 0.2 part of defoaming agent, 4.5 parts of film forming additive and 0.3 part of neutralizing agent into 8.5 parts of water solvent, and respectively stirring at low speed for 10 minutes without splashing the materials;
slowly adding 45 parts of pigment and filler, taking care not to cause serious dust emission and powder accumulation, and washing the powder on the wall of the cylinder with a small amount of clear water; dispersing for 10-15 minutes at a high speed, then placing the mixture into a sand mill, grinding the mixture to a fineness of less than 30 micrometers, placing the mixture into a paint mixing kettle, washing a pull cylinder and the sand mill by using the residual deionized water, and placing the washing liquid into the paint mixing kettle after sand milling;
step 3, adding the graphene oxide composite emulsion into a paint mixing kettle, slowly adding 1 part of flash rust resisting auxiliary agent and 1 part of rheological auxiliary agent, respectively stirring at a low speed for 10 minutes without splashing the materials, adding water to adjust to a proper viscosity, and stirring at a low speed for 5-10 minutes until no obvious bubbles exist;
and 4, filtering and packaging to obtain the water-based composite anticorrosive paint.
Referring to Table 3, Table 3 shows the specific formulations and components of examples 4-6 of the present invention and comparative example 1.
TABLE 3
The performance of the aqueous composite anticorrosive paint prepared in the embodiment 4 of the invention is detected.
Drying time test method: the surface stem is carried out according to the regulation of the surface stem B method in GB/T1728-1979, and the actual stem is carried out according to the regulation of the actual stem A method in GB/T1728-1979.
Water resistance test method: the method is carried out according to the regulation of 9.1 in GB/T1733-1933.
The salt spray resistance performance test method comprises the following steps: the method is carried out according to the regulation of GB/T1771-2007.
The detection results are shown in table 4, and table 4 shows performance detection results of the water-based composite anticorrosive coatings prepared in examples 4 to 6 of the invention and the water-based anticorrosive coating prepared in comparative example 1.
TABLE 4
| Example 4 | Example 5 | Example 6 | Comparative example 1 | |
| Watch stem | 0.5 | 0.5 | 0.5 | 0.5 |
| Dried bean curd | 24 | 24 | 24 | 24 |
| Water resistance | 650h | 800h | 720h | 120h |
| Salt fog resistance | 456h | 502h | 480h | 48h |
The paint film of the water-based composite anticorrosive paint prepared in the embodiment 4 of the invention is characterized.
Referring to fig. 1, fig. 1 is an SEM scanning electron microscope image of a paint film section of the water-based composite anticorrosive paint prepared in example 4 of the present invention.
Referring to fig. 2, fig. 2 is a scanning electron microscope image of a paint film section of the water-based composite anticorrosive paint prepared in example 4 of the invention.
As can be seen from FIG. 1, in the paint film of the water-based composite anticorrosive paint prepared by the invention, graphene oxide sheets are embedded in a paint polymer formed by crosslinking an acrylic polymerization monomer and a crosslinking monomer, the sheet layer integrity is high, the sheet layer thickness is thin, and agglomeration and superposition do not occur.
As can be seen from FIG. 2, in the paint film of the water-based composite anticorrosive paint prepared by the invention, graphene oxide sheets are flatly, uniformly and orderly arranged in the paint film structure to form a graphene oxide layer. And the graphene oxide sheets are distributed in a parallel-like staggered manner to form a labyrinth network interwoven by graphene oxide sheets, and the graphene oxide sheets are embedded in a coating polymer formed by crosslinking an acrylic polymerization monomer and a crosslinking monomer. But also from the upper surface of the paint film to the lower surface of the paint film. The plane of the graphene oxide layer is substantially the same as the plane of the paint film. In the present invention, the thickness direction of the graphene oxide layer is substantially the same as the thickness direction of the paint film structure. With reference to fig. 1, the microscopic two-dimensional lamellar structure of the graphene oxide sheet in the paint film is combined with the macroscopically formed graphene oxide layer, so that the physical barrier and static conductive capability is favorably formed, and the corrosion resistance and the conductivity of the paint are improved.
Example 5
The graphite oxide allyl acid emulsion prepared in the embodiment 2 of the invention is adopted.
Step 1, adding 3.2 parts of dispersing agent, 0.21 part of wetting agent, 0.23 part of defoaming agent, 6 parts of film forming additive and 0.42 part of neutralizing agent into 10.2 parts of water solvent, and respectively stirring at low speed for 10 minutes without splashing the materials;
slowly adding 45 parts of pigment and filler, taking care not to cause serious dust emission and powder accumulation, and washing the powder on the wall of the cylinder with a small amount of clear water; dispersing for 10-15 minutes at a high speed, then feeding the mixture into a sand mill, grinding the mixture to a fineness of less than 30um, feeding the mixture into a paint mixing kettle, cleaning a pull cylinder and the sand mill by using the residual deionized water, and feeding the cleaning solution into the paint mixing kettle after sand milling;
step 3, adding the graphene oxide composite emulsion into a paint mixing kettle, slowly adding 1.3 parts of flash rust resisting auxiliary agent and 1.5 parts of rheological auxiliary agent, respectively stirring at a low speed for 10 minutes without splashing the materials, adding water to adjust to a proper viscosity, and stirring at a low speed for 5-10 minutes until no obvious bubbles exist;
and 4, filtering and packaging to obtain the water-based composite anticorrosive paint.
Referring to Table 3, Table 3 shows the specific formulations and components of examples 4-6 of the present invention and comparative example 1.
The performance of the aqueous composite anticorrosive paint prepared in the embodiment 5 of the invention is detected.
The detection results are shown in table 4, and table 4 shows performance detection results of the water-based composite anticorrosive coatings prepared in examples 4 to 6 of the invention and the water-based anticorrosive coating prepared in comparative example 1.
The paint film of the water-based composite anticorrosive paint prepared in the embodiment 5 of the invention is characterized.
Referring to fig. 3, fig. 3 is an SEM scanning electron microscope image of a paint film section of the water-based composite anticorrosive paint prepared in example 5 of the present invention.
As can be seen from FIG. 3, in the paint film of the water-based composite anticorrosive paint prepared by the invention, the graphene oxide sheets are embedded in the paint polymer formed by crosslinking the acrylic polymer monomer and the crosslinking monomer, the sheet layer integrity is high, the sheet layer thickness is thin, and no agglomeration or superposition exists. And the graphene oxide sheets are evenly and orderly arranged in the paint film structure to form the graphene oxide layer. And the graphene oxide sheets are distributed in a parallel-like staggered manner to form a labyrinth network with interwoven graphene oxide sheets.
Example 6
The graphite oxide allyl acid emulsion prepared in example 3 of the present invention was used.
Step 1, adding 3.4 parts of dispersing agent, 0.19 part of wetting agent, 0.31 part of defoaming agent, 5.3 parts of film forming additive and 0.52 part of neutralizing agent into 13.6 parts of water solvent, and respectively stirring at low speed for 10 minutes without splashing the materials;
slowly adding 45 parts of pigment and filler, taking care not to cause serious dust emission and powder accumulation, and washing the powder on the wall of the cylinder with a small amount of clear water; dispersing for 10-15 minutes at a high speed, then feeding the mixture into a sand mill, grinding the mixture to a fineness of less than 30um, feeding the mixture into a paint mixing kettle, cleaning a pull cylinder and the sand mill by using the residual deionized water, and feeding the cleaning solution into the paint mixing kettle after sand milling;
step 3, adding the graphene oxide composite emulsion into a paint mixing kettle, slowly adding 1.5 parts of flash rust resisting auxiliary agent and 2 parts of rheological auxiliary agent, respectively stirring at a low speed for 10 minutes without splashing the materials, adding water to adjust to a proper viscosity, and stirring at a low speed for 5-10 minutes until no obvious bubbles exist;
and 4, filtering and packaging to obtain the water-based composite anticorrosive paint.
Referring to Table 3, Table 3 shows the specific formulations and components of examples 4-6 of the present invention and comparative example 1.
The performance of the aqueous composite anticorrosive paint prepared in the embodiment 6 of the invention is detected.
The detection results are shown in table 4, and table 4 shows performance detection results of the water-based composite anticorrosive coatings prepared in examples 4 to 6 of the invention and the water-based anticorrosive coating prepared in comparative example 1.
The paint film of the water-based composite anticorrosive paint prepared in the embodiment 6 of the invention is characterized.
Referring to fig. 4, fig. 4 is an SEM scanning electron microscope image of a paint film section of the water-based composite anticorrosive paint prepared in example 6 of the present invention.
As can be seen from fig. 4, in the paint film of the aqueous composite anticorrosive paint prepared by the present invention, the graphene oxide sheets are embedded in the paint polymer formed by crosslinking the acrylic polymeric monomer and the crosslinking monomer, and are not agglomerated and stacked. And the graphene oxide sheets are evenly and orderly arranged in the paint film structure to form the graphene oxide layer. And the graphene oxide sheets are distributed in a parallel-like staggered manner to form a labyrinth network with interwoven graphene oxide sheets. The graphene oxide lamellae are embedded in a coating polymer formed after crosslinking of the acrylic polymeric monomer and the crosslinking monomer. But also from the upper surface of the paint film to the lower surface of the paint film. The plane of the graphene oxide layer is substantially the same as the plane of the paint film. The thickness direction of the graphene oxide layer is substantially the same as the thickness direction of the paint film structure. With reference to fig. 1, the microscopic two-dimensional lamellar structure of the graphene oxide sheet in the paint film is combined with the graphene oxide layer formed macroscopically, so that a physical barrier layer is formed between the metal matrix and the active medium, the physical barrier and static electricity conducting capabilities are favorably formed, and the corrosion resistance and the electric conductivity of the paint are improved.
Comparative example 1
Step 1, adding 3.1 parts of dispersing agent, 0.21 part of wetting agent, 0.25 part of defoaming agent, 4.9 parts of film forming additive and 0.48 part of neutralizing agent into 10 parts of water solvent, and respectively stirring at low speed for 10 minutes without splashing the materials;
slowly adding 45 parts of pigment and filler, taking care not to cause serious dust emission and powder accumulation, and washing the powder on the wall of the cylinder with a small amount of clear water; dispersing for 10-15 minutes at a high speed, then feeding the mixture into a sand mill, grinding the mixture to a fineness of less than 30um, feeding the mixture into a paint mixing kettle, cleaning a pull cylinder and the sand mill by using the residual deionized water, and feeding the cleaning solution into the paint mixing kettle after sand milling;
and 3, adding the acrylic emulsion into the paint mixing kettle, slowly adding 1.2 parts of flash rust resisting auxiliary agent and 1.8 parts of rheological auxiliary agent, respectively stirring at a low speed for 10 minutes without splashing the materials, adding water to adjust to a proper viscosity, and stirring at a low speed for 5-10 minutes until no obvious bubbles exist, thereby obtaining the water-based acrylic anticorrosive paint.
Referring to Table 3, Table 3 shows the specific formulations and components of examples 4-6 of the present invention and comparative example 1.
The performance of the aqueous anticorrosive paint prepared in comparative example 1 of the present invention was tested.
The detection results are shown in table 4, and table 4 shows performance detection results of the water-based composite anticorrosive coatings prepared in examples 4 to 6 of the invention and the water-based anticorrosive coating prepared in comparative example 1.
The above detailed description of the present invention provides a water-based composite anticorrosive paint film, a water-based graphene oxide composite anticorrosive paint and a preparation method thereof, and the principle and embodiments of the present invention are described herein by using specific examples, which are provided only for helping to understand the method and the core idea of the present invention, including the best mode, and also for enabling any person skilled in the art to practice the present invention, including making and using any device or system, and implementing any combined method. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.
Claims (10)
1. A water-based composite anticorrosive paint film is characterized in that graphene oxide sheets are uniformly and orderly arranged in the paint film structure to form a graphene oxide layer;
the graphene oxide layer is in the paint film structure;
the thickness direction of the graphene oxide layer is the same as or similar to the thickness direction of the paint film structure.
2. The paint film of claim 1, wherein adjacent or similar graphene oxide sheets in the graphene oxide layer are staggered in a thickness direction of the graphene oxide layer as viewed in a section of the paint film structure;
viewed from the section of the paint film structure, a graphene oxide layer with a labyrinth effect is formed between the graphene oxide sheets along the thickness direction of the graphene oxide layer;
the thickness directions are close, namely, the included angle between the thickness direction of the graphene oxide layer and the thickness direction of the paint film structure is less than or equal to 60 degrees;
the thickness of the graphene oxide sheet is 0.7-2 nm;
the number of graphene oxide sheets is 1-5;
the thickness of the paint film is 50-100 mu m.
3. The water-based composite anticorrosive paint is characterized by comprising the following components in percentage by mass:
4. the water-based composite anticorrosive paint according to claim 3, wherein the auxiliary agent comprises one or more of a dispersant, a wetting agent, a defoaming agent, a neutralizing agent, a film-forming auxiliary agent, an anti-flash rust auxiliary agent and a rheological auxiliary agent;
the addition amount of the dispersing agent is 1-5 parts by weight;
the addition amount of the wetting agent is 0.05-0.3 part by weight;
the addition amount of the defoaming agent is 0.1-0.5 part by weight;
the addition amount of the neutralizing agent is 0.3-0.6 part by weight;
the addition amount of the film-forming assistant is 3-8 parts by weight;
the flash rust resisting additive is added in an amount of 0.5-2 parts by weight;
the addition amount of the rheological additive is 0.5-2 parts by weight;
the mass content of the graphene oxide in the water-based composite anticorrosive paint is 0.1-3%;
the dispersant comprises one or more of KALD-104, KOOLY 756, KOOLY7166, Silok7195W and OROTAN 731A;
the wetting agent comprises one or more of TEGO Twin4100, CA-81, KSPW-101 and KSPW-132;
the antifoaming agent comprises one or more of TEGO 902w, TEGO 1488, KXDF-204, BYK-024, and KOOLY 3150;
the neutralizing agent AMP-95 and/or ammonia water;
the film forming auxiliary agent comprises one or more of DPM, DPnB and texnol;
the flash rust resisting auxiliary agent comprises one or more of initiator R-760F, Hostacor AC 18, Raybo 60, Lubrizol 2120 and SHYT 5179;
the rheological additive comprises one or more of RM-8W, RM-2020, RM-12W and KTGF-132;
the pigment and filler comprises one or more of zinc powder, iron oxide red, coarse whiting powder, titanium dioxide, antirust pigment, talcum powder, barite powder and mica powder.
5. The aqueous composite anticorrosive paint according to claim 4, wherein the graphene oxide allyl acid emulsion comprises graphene oxide, an acrylic polymer monomer and a crosslinking monomer;
in a paint film of the water-based composite anticorrosive paint, the graphene oxide is embedded in a polymer formed by crosslinking the acrylic polymerization monomer and the crosslinking monomer;
the crosslinking monomer comprises an amide group-containing crosslinking monomer;
the graphite oxide allyl acid emulsion comprises the following components in percentage by mass:
6. the aqueous composite anticorrosive coating according to claim 5, wherein the acrylic polymeric monomer comprises one or more of acrylic acid, methacrylic acid, acrylate ester and methacrylate ester;
the crosslinking monomer comprises one or more of acrylamide, N-methylolacrylamide and N, N-diacetone acrylamide;
the protective glue comprises one or more of polyvinyl alcohol, styrene-maleic anhydride copolymer, acrylate copolymer and acrylic acid-styrene copolymer;
the initiator comprises one or more of inorganic peroxide initiator, organic peroxide initiator, azo initiator and redox initiator;
the emulsifier comprises a reactive emulsifier and an anionic emulsifier.
7. The aqueous composite anticorrosive paint according to claim 5, wherein the acrylic polymeric monomer comprises one or more of acrylic acid, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, isooctyl methacrylate, and isobornyl methacrylate;
the initiator comprises one or more of potassium persulfate, ammonium persulfate, benzoyl peroxide, tert-butyl hydroperoxide and azobisisobutyronitrile;
the anionic emulsifier comprises one or more of carboxylate, sulfonate and sulfate;
the reactive emulsifier comprises one or more of acrylamide isopropyl sodium sulfonate, sulfate containing vinyl alcohol ether, sodium succinate containing vinyl alcohol ether sulfonic group and sodium hydroxy alkyl sulfonate containing vinyl ether;
the content of the graphene oxide in the aqueous graphene oxide dispersion liquid is 1-5%.
8. The preparation method of the water-based composite anticorrosive paint is characterized by comprising the following steps of:
A) mixing a part of auxiliary agent and water, then adding pigment and filler, mixing again, and then grinding to obtain slurry;
B) and continuously mixing the slurry obtained in the step, the oxidized graphite allyl acrylic acid emulsion, the other part of the auxiliary agent and water to obtain the water-based composite anticorrosive paint.
9. The method of claim 8, wherein the portion of the auxiliary agent includes one or more of a dispersant, a wetting agent, a defoamer, a film-forming auxiliary agent, and a neutralizer;
the other part of the auxiliary agent comprises an anti-flash rust auxiliary agent and/or a rheological auxiliary agent;
the mixing comprises stirring and mixing at a low speed;
the mixing time is 5-15 minutes;
the mixing speed is 500-800 r/min;
the remixing comprises high-speed stirring and mixing;
the remixing time is 10-15 minutes;
the rotation speed of the remixing is 800-1200 r/min.
10. The method according to claim 8, wherein the grinding time is 10 to 15 minutes;
the rotation speed of the grinding is 600-900 r/min;
the particle size after grinding is less than or equal to 30 mu m;
the continuous mixing comprises low-speed stirring and mixing;
the time for continuing mixing is 10-25 minutes;
the rotating speed of the continuous mixing is 600-800 r/min;
the viscosity of the water-based composite anticorrosive paint is 80-105 ku.
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